A new strategy for inducing dipole moments in charge-transfer complexes: introduction of asymmetry into axially ligated iron phthalocyanines.

Introduction of asymmetry into charge-transfer complexes composed of axially ligated iron phthalocyanines was achieved. In the obtained crystals of TPP[FeIII(Pc)(CN)Cl]2, TPP[FeIII(Pc)(CN)Br]2, and TPP[FeIII(Pc)BrCl]2 (TPP = tetraphenylphosphonium and Pc = phthalocyanine), the axial positions of the iron atoms were occupied by 50/50 ratios of the ligands CN/Cl, CN/Br, and Br/Cl, respectively. The crystal structures of the obtained CT complexes were isostructural to those composed of the symmetric analogues of the type [FeIII(Pc)L2] (L = CN, Cl or Br); the [FeIII(Pc)LL'] units formed regular one-dimensional chains along the c-axis following the symmetry of the P42/n space group. Despite forming similar regular chains to the symmetric systems, the electrical resistivities and activation energies were enhanced in the obtained CT complexes compared to those in symmetric systems, indicating that the charge-ordered states were stabilised by the introduction of asymmetry. More specifically, the dielectric relaxation behaviour of the inhomogeneous disordered TPP[FeIII(Pc)(CN)Cl]2 probably suggests that a dipole moment was induced in this material.

Cinacalcet hydrochloride relieves hypercalcemia in Japanese patients with parathyroid cancer and intractable primary hyperparathyroidism.

Pharmacological treatment of hypercalcemia is essential for patients with parathyroid carcinoma and intractable primary hyperparathyroidism (PHPT). Use of the calcimimetic cinacalcet hydrochloride (cinacalcet) is an option to treat such patients. We investigated the efficacy and safety of cinacalcet in Japanese patients with parathyroid carcinoma and intractable PHPT. Five Japanese patients with parathyroid carcinoma and two with intractable PHPT were enrolled in an open-label, single-arm study consisting of titration and maintenance phases. Cinacalcet doses were titrated until the albumin-corrected serum calcium concentration decreased to 10.0 mg/dL or less or until dose escalation was considered not necessary or feasible. Serum calcium concentration at the baseline was 12.1 ± 1.3 mg/dL (mean ± standard deviation; range 10.4-14.6 mg/dL) and decreased to 10.1 ± 1.6 mg/dL (range 8.6-13.3 mg/dL) at the end of the titration phase with cinacalcet at a dosage of up to 75 mg three times a day. At the end of the titration phase, at least a 1 mg/dL reduction in serum calcium concentration from the baseline was observed in five patients (three with carcinoma and two with PHPT), and it decreased to the normocalcemic range in five patients (three with carcinoma and two with PHPT). Common adverse events were nausea and vomiting. One patient discontinued participation in the study because of an adverse event, liver disorder. Cinacalcet effectively relieved hypercalcemia in 60% of the Japanese patients with parathyroid carcinoma and might be effective in those with intractable PHPT. The drug might be tolerable and safe at a dosage of at most 75 mg three times a day.

Cortical field potentials preceding self-paced forelimb movements and influences of cerebellectomy upon them in rats.

Seven rats were well trained to move lever to the left by right forelimb at self-pace (self-paced forelimb movements). Cortical field potentials associated with self-paced forelimb movements were recorded by electrodes implanted chronically on the surface and at a 2.0 mm depth in the forelimb motor cortex on the left side. A surface-negative, depth-positive potential starting about 1.0 s prior to the movement was recorded in the rostral part of the forelimb motor cortex. Further we found that the premovement potential was eliminated by the cerebellar hemispherectomy on the right side. This suggests the participation of the cerebellar hemisphere in preparing the activity of the motor cortex before self-paced forelimb movements in rats, by cerebello-thalamo-cortical projections.